CN108699673A

CN108699673A - The manufacturing method of copper foil with carrier and centreless supporter and printed circuit board with wiring layer

Info

Publication number: CN108699673A
Application number: CN201780014211.2A
Authority: CN
Inventors: 松浦宜范
Original assignee: Mitsui Mining and Smelting Co Ltd
Current assignee: Mitsui Mining and Smelting Co Ltd
Priority date: 2016-02-29
Filing date: 2017-02-21
Publication date: 2018-10-23
Anticipated expiration: 2037-02-21
Also published as: CN111787714A; KR20180113580A; KR20200142121A; US20190029125A1; WO2017150284A1; US20200053885A1; TW202111906A; WO2017149811A1; US10492308B2; CN108699673B; JP6883010B2; US10888003B2; JPWO2017150284A1; JP2019031739A; KR102550963B1; TW201742225A; TWI709215B; JP6415760B2; US10356915B2; US20190261518A1

Abstract

It provides:Excellent peel resistance is presented to developer solution in development of photoresist process and the excellent stability of the mechanical stripping intensity of carrier, copper foil with carrier can be brought.The copper foil with carrier has:Carrier;Middle layer is set on carrier, and at least one kind of metal in the group being made of Ti, Cr, Mo, Mn, W and Ni of 1.0at% or more is contained on the surface of carrier side, and contains the Cu of 30at% or more with the surface of carrier opposite side;Peeling layer is set in middle layer;With very thin layers of copper is set on peeling layer.

Description

Copper foil with carrier and the centreless supporter with wiring layer and printed circuit board Manufacturing method

Technical field

The manufacturer of centreless supporter and printed circuit board the present invention relates to the copper foil with carrier and with wiring layer Method.

Background technology

In recent years, in order to improve packing density and the miniaturization of printed circuit board, printed circuit board has been carried out extensively Multiple stratification.Such multilayer board in movement electronic equipment mostly in order to lightweight, miniaturization and utilize.And And the multilayer board requires the thickness of interlayer insulating film to further decrease and as the further light of circuit board Quantization.

As the technology required as satisfaction, the manufacturer of the multilayer board using centreless lamination method is used Method.Centreless lamination method refers to, without using so-called core substrate, simultaneously with wiring layer alternately laminated (lamination) by insulating layer The method of multiple stratification.In centreless lamination method, it is proposed that the copper foil with carrier is used, so that supporter and multilayer board Stripping can be easy to carry out.For example, disclosing a kind of semiconductor element in patent document 1 (Japanese Unexamined Patent Publication 2005-101137 bulletins) The manufacturing method of part package for mounting substrate comprising:Branch is formed in the carrier side adherency insulating resin layer of the copper foil with carrier Support body, by processes such as photoresist processing, pattern electro-coppering, resist removals in the very thin layers of copper side of the copper foil with carrier The first wiring conductor is formed, build-up wiring layer is then formed, the supporting substrate with carrier is removed, very thin layers of copper is removed.

However, in order to shown in patent document 1 be embedded to circuit miniaturization, it is expected that make very thin layers of copper thickness be 1 μm with Under the copper foil with carrier.Therefore, in order to realize very thin layers of copper thickness reduce, it is proposed that very thin layers of copper is formed by vapor phase method Scheme.For example, a kind of copper foil with carrier-pellet is disclosed in patent document 2 (No. 4726855 bulletins of Japanese Patent No.), The surface of carrier-pellet has copper foil layer across joint interface layer, discloses:The joint interface layer using physical vapor deposition by being formed This 2 layers of metal layer (carrier-pellet side)/carbon-coating (very thin layers of copper side) composition, copper foil layer obtains as follows:It is used on joint interface layer Physical vapor deposition forms the 1st layers of copper of thickness 10nm~300nm, and then forms the 2nd layers of copper with electrolysis, to obtain.In addition, In patent document 2 record, the metal layer for constituting the joint interface layer can be by tantalum, niobium, zirconium, nickel, chromium, titanium, iron, silicon, molybdenum, The layer that any one of vanadium, tungsten are constituted.

In addition, disclosing a kind of copper foil with carrier in patent document 3 (No. 4072431 bulletins of Japanese Patent No.), it is The peeling layer of promising layers of chrome, easy absorption CO are stacked gradually on the surface of carrier foils₂The layer of the light of the wavelength of gas laser oscillation It i.e. made of barrier layer and copper electroplating layer, discloses, barrier layer is by being selected from by nickel, cobalt, iron, molybdenum, tungsten, aluminium and phosphorus group At group in the layer of single metal that is formed of element or to be made of nickel, cobalt, iron, chromium, molybdenum, tungsten, copper, aluminium and phosphorus by being selected from Group in element the alloy-layer that is formed of metal of more than two kinds or a kind or more of metal oxide layer.

Existing technical literature

Patent document

Patent document 1:Japanese Unexamined Patent Publication 2005-101137 bulletins

Patent document 2:No. 4726855 bulletins of Japanese Patent No.

Patent document 3:No. 4072431 bulletins of Japanese Patent No.

Patent document 4:Japanese Unexamined Patent Publication 2015-35551 bulletins

Invention content

However, (fan-out-type wafer stage chip encapsulates (Fan- to the FO-WLP of one of encapsulation technology as printed circuit board Out Wafer Level Packaging)), (panel grade is fanned out to encapsulation (Fan-Out Panel Level to FO-PLP Packaging it in)), also studied using centreless lamination method.As one of such technique, has and following be referred to as RDL- The technique of First (Redistribution Layer-First) method:Wiring layer is formed in centreless supporting body surface and according to need The build-up wiring layer wanted, and then after as needed removing supporter, the installation of chip is carried out (referring for example to 4 (day of patent document This special open 2015-35551 bulletins)).According to the technique, before carrying out chip installation, body surface is supported since centreless can be carried out The image inspection of the wiring layer in face, each build-up wiring layer being laminated later, it can thus be avoided the bad part of each wiring layer, Only in non-defective unit part chip.As a result, can to avoid the unnecessary for the use of of chip, RDL-First methods with The technique i.e. Chip-First methods etc. that wiring layer is stacked gradually on the surface of chip is compared, and is economically advantageous.Herein, it is Image inspection is carried out after the wiring layer for just forming centreless supporting body surface, and photoresist is carried out in centreless supporting body surface After agent processing, plating and photoresist stripping etc., and then the quick of the very thin layers of copper being present between wiring is carried out as needed After etching, the carrying of the electronic components such as chip is carried out as needed, carries out the formation of lamination layer later.However, due to carrying core Along with heating when the electronic components such as piece, therefore, have the problem of easy ting produce warpage on centreless supporter.This is asked in order to prevent Topic considers that material i.e. glass, ceramics, low thermal expansion resin for using coefficient of thermal expansion (CTE) low etc. are used as carrier.However, making It uses such low thermal expansion material as in the case of carrier, there is the problem of carrier accidentally becomes easy stripping.The problem It is particularly significant in the case where peeling layer is carbon-coating.Accordingly, it is considered to be arranged for improving adaptation between peeling layer and carrier Layer, but the peel strength of carrier becomes unstable at this time, and centreless supporter is difficult to steadily remove carrier when detaching.In this way, There is following problem:The desired mechanical stripping intensity of carrier can not be stably obtained, that is, the mechanical stripping intensity of carrier is unstable It is fixed.On the other hand, for the copper foil with carrier, in the development of photoresist process for the wiring layer for forming centreless supporting body surface In (such as using aqueous sodium carbonate as the process of developer solution), also it is desirable to peel resistance be presented.

The inventors of the present invention obtain following opinion this time:Pass through the sandwiched between the carrier and peeling layer of the copper foil with carrier The middle layer being made of defined metal can be provided in and excellent resistance to stripping is presented in development of photoresist process to developer solution From property and excellent stability, copper foil with carrier can be come for the mechanical stripping intensity band of carrier.

Therefore, the object of the present invention is to provide:Excellent resistance to stripping is presented in development of photoresist process to developer solution From property and excellent stability, copper foil with carrier can be come for the mechanical stripping intensity band of carrier.

A mode according to the present invention provides a kind of copper foil with carrier, has:

Carrier;

Middle layer is set in aforementioned bearer, the surface of aforementioned bearer side contain 1.0at% or more selected from by Ti, At least one kind of metal in the group of Cr, Mo, Mn, W and Ni composition, and contain 30at% or more with the surface of aforementioned bearer opposite side Cu;

Peeling layer is set in aforementioned middle layer;With,

Very thin layers of copper is set on aforementioned peeling layer.

Another way according to the present invention provides a kind of manufacturing method of the centreless supporter with wiring layer comprising such as Lower process:

Prepare process of the copper foil with carrier of aforesaid way as supporter;

In the process that the surface of aforementioned very thin layers of copper forms photoresist layer with defined pattern;

In the process that the exposing surface of aforementioned very thin layers of copper forms copper electroplating layer;

The process that aforementioned photoresist layer is removed;With,

The unwanted part of aforementioned very thin layers of copper is removed by copper fast-etching, obtains the centreless for being formed with wiring layer The process of supporter.

Another way according to the present invention provides a kind of manufacturing method of printed circuit board comprising following process:

The process of the centreless supporter of method manufacture aforementioned strip wiring layer through the above way;

Have in the formation of the centreless supporter of aforementioned strip wiring layer and form lamination layer on the face of aforementioned wiring layer, makes band product The process of laminated body layer by layer;

By the aforementioned stripping layer separation of the laminated body of aforementioned strip lamination layer, the multilayer circuit board for including aforementioned lamination layer is obtained Process;With,

Aforenoted multi-layer circuit board is processed to obtain the process of printed circuit board.

Description of the drawings

Fig. 1 is the constructed profile for the mode for showing the copper foil with carrier of the present invention.

Fig. 2 is the constructed profile for the another way for showing the copper foil with carrier of the present invention.

Fig. 3 is the process of the manufacturing method of the centreless supporter or printed circuit board with wiring layer for illustrating the present invention Flow chart, for show first half process (process (a)~(c)) figure.

Fig. 4 is the process of the manufacturing method of the centreless supporter or printed circuit board with wiring layer for illustrating the present invention Flow chart, for show then Fig. 3 process (process (d)~(f)) figure.

Fig. 5 is the process flow chart of the manufacturing method of the printed circuit board for illustrating the present invention, to show then Fig. 4's The figure of process (process (g)~(i)).

Specific implementation mode

Copper foil with carrier

The copper foil with carrier of the present invention is schematically shown in Fig. 1.As shown in Figure 1, the copper of the invention with carrier Foil 10 has carrier 12, middle layer 14, peeling layer 16 and very thin layers of copper 18 successively.Middle layer 14 is such as lower layer:It is set to carrier On 12, at least 1 in the group being made of Ti, Cr, Mo, Mn, W and Ni of 1.0at% or more is contained on the surface of carrier 12 side Kind metal and the Cu for containing 30at% or more with the surface of carrier 12 opposite side.Peeling layer 16 is disposed in middle layer 14 Layer.Very thin layers of copper 18 is disposed on layer on peeling layer 16, being made of copper.According to expectation, the copper foil of the invention with carrier 10 can further have anti-reflection layer 17 between peeling layer 16 and very thin layers of copper 18.Furthermore it is possible to form following composition:With Have above-mentioned various layers successively on the two sides of carrier 12 as mode symmetrical above and below.Copper foil 10 with carrier, which removes, to be had among the above Interbed 14 and according to desired anti-reflection layer 17 except, as long as using well known layer constitute as long as be not particularly limited.

In this way, by between the carrier 12 and peeling layer 16 of the copper foil 10 with carrier sandwiched be made of defined metal Developer solution is presented in development of photoresist process excellent peel resistance in middle layer 14, and can be the machinery stripping of carrier The break-off of the middle layer generated when carrying out excellent stability from intensity band, prevent centreless supporter or carrier stripping, from And generate excellent wiring pattern formative.That is, the mechanism that middle layer 14 plays said effect not yet determines, but can examine as follows Consider.That is, constitute middle layer 14 with carrier 12 opposite side (that is, 16 side of peeling layer) although surface copper can with constitute remove Assign low adaptation between the material (such as carbon) of layer 16, be conducive to stable stripping, but then, carrier (such as Glass, ceramics) between adaptation and fissility may become unstable.For the problem, it is believed that by the load for making middle layer 14 At least one kind of metal in the group being made of Ti, Cr, Mo, Mn, W and Ni of 1.0at% or more is contained on the surface of 12 side of body, Convenient for assigning excellent stripping stability between middle layer 14 and carrier 12 and to the peel resistance of developer solution.

The material of carrier 12 can be any one of glass, ceramics, resin and metal.In addition, the form of carrier 12 can be with For any one of piece, film, plate and foil.In addition, carrier 12 can be will be obtained from the stackings such as these pieces, film, plate and foil Substance.For example, carrier 12 can function in the form of glass plate, ceramic wafer, metallic plate etc. have the supporter of rigidity, It can be the form that metal foil, resin film etc. do not have rigidity.The preference of metal as carrier 12, can enumerate copper, Titanium, nickel, stainless steel, aluminium etc..As the preference of ceramics, aluminium oxide, zirconium oxide, silicon nitride, aluminium nitride and each can be enumerated Kind fine ceramics etc..As the preference of resin, PET resin, PEN resins, aromatic polyamide resin, polyimides can be enumerated Resin, liquid crystal polymer, PEEK resins, polyimide resin, polyamide-imide resin, polyethersulfone resin, gathers nylon resin Diphenyl sulfide resin, PTFE resin, ETFE resins etc..From heating when preventing from carrying electronic component with centreless supporter From the perspective of warpage, material of the more preferable coefficient of thermal expansion (CTE) less than 25ppm/K (typically 1.0~23ppm/K), As the example of such material, can enumerating above-mentioned various resins, (especially polyimide resin, liquid crystal polymer etc. are low Thermally expand resin), glass and ceramics etc..In addition, from the viewpoint of operability, ensure chip install when flatness, carrier 12 preferred Vickers hardnesses are 100HV or more, more preferable 150~2500HV.As the material for meeting these characteristics, carrier 12 is preferred It is made of resin film, glass or ceramics, is more preferably made of glass or ceramics, be particularly preferably made of glass.For example, glass Glass piece.When using glass as carrier 12, have the following advantages:Light weight, coefficient of thermal expansion is low, and insulating properties is high, due to upright and outspoken and table Face is flat therefore the surface of very thin layers of copper 18 can be made extremely smooth etc..In addition, when carrier is glass, have the following advantages:Form nothing It is excellent with the identification contrast of copper plate when carrying out image inspection after the wiring layer of core supporting body surface;Carry electronic component When have advantageous surface (coplanarity);In desmearing, various plating process in printed circuit board manufacturing process With chemical resistance;The aftermentioned laminated body with lamination layer can use fractionation etc. when detaching.As composition carrier The preference of 12 glass can enumerate quartz glass, borosilicate glass, alkali-free glass, soda-lime glass, aminosilicates glass Glass and combination thereof, particularly preferably alkali-free glass.Alkali-free glass is with silica, aluminium oxide, boron oxide and oxidation The alkaline earth oxides such as calcium, barium monoxide be principal component so that containing boric acid, the glass that contains substantially no alkali metal.It should It is alkali-free glass in the range of coefficient of thermal expansion is in 3~5ppm/K in 0 DEG C~350 DEG C of wider temperature band, low and stablize, because This, when carrying the semiconductor chip as electronic component, there is the advantages of warpage of glass can be made to be bottom line.The thickness of carrier It is preferred that 100~2000 μm, it is 300~1800 μm more preferable, 400~1100 μm further preferred.For the thickness in such range When, it can be ensured that it will not be the intensity appropriate that operation brings obstacle, and can realize slimming and the drop of printed circuit board The warpage generated when low electro part carrying.

The surface of 14 side of middle layer of carrier 12 preferably has being measured according to JIS B 0601-2001,0.1~70nm Arithmetic average roughness Ra, more preferable 0.5~60nm, further preferred 1.0~50nm, particularly preferred 1.5~40nm, most preferably 2.0~30nm.In this way, arithmetic average roughness is smaller, it more can be in the surface (pole with 16 opposite side of peeling layer of very thin layers of copper 18 The outer surface of thin copper layer 18) desired low arithmetic average roughness Ra is assigned, use the copper foil 10 with carrier to manufacture as a result, In printed circuit board, suitably form high fineization until line/space (L/S) be 13 μm or less/13 μm or less (such as 12 μm/ 12 μm~2 μm/2 μm) etc degree wiring pattern.

From the adaptation aspect for ensuring carrier 12 and middle layer 14, the surface of the carrier 12 side of middle layer 14 be containing By the metal of at least one kind of metal (hereinafter referred to as metal M) in the group being made of Ti, Cr, Mo, Mn, W and Ni.Middle layer The containing ratio of metal M in the surface of 14 carrier 12 side preferably 1.0 atom % or more, more preferable 3.0 atom % or more, into one Walk preferably 4.0 atom % or more.The metal can be simple metal, or alloy.Therefore, the containing ratio of above-mentioned metal M The upper limit is not particularly limited, and can be 100 atom %.On the other hand, middle layer 14 with the surface of carrier 12 opposite side be containing There is the metal of Cu.From keep with the release performance aspect of peeling layer, middle layer 14 with carrier 12 opposite side (that is, stripping 16 side of absciss layer) surface in Cu containing ratios preferably 30 atom % or more, more preferable 40 atom % or more, further preferred 50 former Sub- % or more.The upper limit of above-mentioned Cu containing ratios is not particularly limited, and can be 100 atom %.

The thickness of middle layer 14 preferably 5~1000nm, more preferable 10~800nm, further preferred 12~500nm, especially It is preferred that 15~400nm.Its thickness is the energy dispersion type X-ray energy spectrum analyzer (TEM-EDX) with transmission electron microscope The value that layer cross section is analyzed to measure.

Middle layer 14 can be 1 layer of composition as shown in Figure 1, can be 2 layers or more of composition as shown in Figure 2.

Preferred embodiment according to the present invention, middle layer 14 is as shown in Figure 2, including closely sealed metal layer 14a and stripping are auxiliary Help a layer 14b.Closely sealed metal layer 14a is disposed on carrier 12 and by the group being made of Ti, Cr, Mo, Mn, W and Ni The layer that at least one kind of metal is constituted.Stripping auxiliary layer 14b is disposed on the layer on closely sealed metal layer 14a and being made of copper.In this way, By combining the closely sealed metal layer 14a being made of defined metal and the stripping auxiliary layer 14b being made of copper and being folded in successively Between the carrier 12 and peeling layer 16 of copper foil 10 with carrier, developer solution can be presented in development of photoresist process excellent Different peel resistance, and excellent stability can be carried out for the mechanical stripping intensity band of carrier.That is, closely sealed metal layer 14a and stripping The mechanism that the combination of auxiliary layer 14b plays said effect not yet determines, but can consider as follows.That is, constituting stripping auxiliary layer 14b Although copper can assign low adaptation between the material (such as carbon) for constituting peeling layer 16, be conducive to stable stripping, But then, between carrier (such as glass, ceramics) adaptation and fissility may become it is unstable be directed to the problem, Think by stripping auxiliary layer 14b and carrier 12 between the closely sealed metal layer 14a of sandwiched, can be convenient for for stripping auxiliary layer 14b with Excellent stripping stability is assigned between carrier 12 and prevents stripping centreless branch to the peel resistance of developer solution, convenient for assigning passing through Excellent wiring pattern formative caused by the break-off of the middle layer generated when support body or carrier.

From the adaptation aspect for ensuring carrier 12 with removing auxiliary layer 14b, closely sealed metal layer 14a is preferably by selecting The layer that at least one kind of metal in the group of free Ti, Cr, Mo, Mn, W and Ni composition is constituted, can be simple metal, or close Gold.Wherein, from ensuring carrier 12 and closely sealed metal layer 14a and remove the adaptation of auxiliary layer 14b, significantly prevent in aftermentioned nothing The stripping of very thin layers of copper in the formation process of core supporter wiring layer, when centreless supporter is removed as the carrier side of generation Metal closely sealed metal layer 14a and stripping auxiliary layer 14b stripping in terms of set out, closely sealed metal layer 14a is most preferably by Ti It constitutes.The metal for constituting closely sealed metal layer 14a can include the inevitable impurity for being originated from material composition, film formation process etc.. In addition, though be not particularly limited, but in the case of be exposed to air after closely sealed metal layer 14a film forming, allow from it and The presence of mixed oxygen.The layer that closely sealed metal layer 14a is formed preferably by vapor phase methods such as sputterings.Divide from film thickness can be improved It sets out in terms of the uniformity of cloth, particularly preferred closely sealed metal layer 14a is formed by using the magnetron sputtering method of metal targets Layer.The thickness of closely sealed metal layer 13 preferably 5~500nm, more preferable 10~300nm, further preferred 18~200nm, especially It is preferred that 20~100nm.The thickness is the energy dispersion type X-ray energy spectrum analyzer (TEM-EDX) with transmission electron microscope The value that layer cross section is analyzed to measure.

It is the layer being made of copper to remove auxiliary layer 14b.The copper for constituting stripping auxiliary layer 14b can include be originated from raw material at Point, the inevitable impurity of film formation process etc..Auxiliary layer 14b is removed in the range of not damaging the fissility of carrier, it can be with Contain at least one kind of metal in the group being made of Si, Al, Ni, Mn, Mg, Nd, Nb, Ag, Zn, Sn, Bi and Fe.Above-mentioned feelings Under condition, stripping auxiliary layer can be described as the layer for mainly including copper.Cu elements from above-mentioned aspect, stripping auxiliary layer 14b Containing ratio preferably 50~100 atom %, more preferable 60~100 atom %, further preferred 70~100 atom %, especially excellent Select 80~100 atom %, most preferably 90~100 atom %.In addition, being exposed to air before and after stripping auxiliary layer 14b film forming In the case of, allow from it and the presence of mixed oxygen.Although being not particularly limited, closely sealed metal layer 14a and stripping it is expected Auxiliary layer 14b continuously forms a film in the case of no atmosphere opening.Auxiliary layer 14b is removed preferably by vapor phase methods such as sputterings The layer of formation.From the uniformity aspect that can improve film thickness distribution, it is by using copper particularly preferably to remove auxiliary layer 14b The layer that the magnetron sputtering method of target is formed.Remove thickness preferably 5~500nm of auxiliary layer 14b, more preferable 10~400nm, into one Walk preferably 15~300nm, particularly preferred 20~200nm.Its thickness is the energy dispersion type X-ray with transmission electron microscope Value of energy spectrum analysis device (TEM-EDX) the analysis layer section to measure.

It should be noted that may exist other sandwiched layers between closely sealed metal layer 14a and stripping auxiliary layer 14b.Make For the example of the constituent material of sandwiched layer, at least one kind of gold in the group being made of Ti, Cr, Mo, Mn, W and Ni can be enumerated Belong to the alloy etc. with Cu.

Another preferred embodiment according to the present invention, as shown in Figure 1, middle layer 14 can be intermediate alloy layer.In that is, Interbed 14 can be set as 1 layer of composition.Middle layer 14 as intermediate alloy layer is preferably by being selected from by Ti, Cr, Mo, Mn, W and Ni The content of at least one kind of metal (hereinafter referred to as metal M) in the group of composition be 1.0at% or more and Cu contents be 30at% with On copper alloy constitute.That is, from the adaptation for ensuring carrier 12 and middle layer 14 and taking into account to the release performance of peeling layer 16 Aspect is set out, and the metal for constituting intermediate alloy layer is preferably the copper alloy of metal M and Cu.Wherein, further preferably be selected from by Ti, The alloy of the metal and Cu of at least one kind of metal in the group of Mo, Mn composition.The containing ratio of metal M in intermediate alloy layer is preferred 1.0 atom % or more, more preferable 3.0 atom % or more, further preferred 5.0 atom % or more.Although in intermediate alloy-layer The upper limit of containing ratio of metal M be not particularly limited, but metal M containing ratios preferably 30 atom % are hereinafter, more preferable 20 is former Sub- % or less.Cu containing ratios preferably 30 atom % or more, more preferable 40 atom % or more in intermediate alloy layer, further preferably 50 atom % or more.Although the upper limit of the containing ratio of the Cu in intermediate alloy-layer is not particularly limited, Cu containing ratios are preferred 99.5 atom % hereinafter, more preferable 97.0 atom % hereinafter, further preferred 96.0 atom % or less.Intermediate alloy layer is preferably The layer formed by vapor phase methods such as sputterings.From the uniformity aspect that can improve film thickness distribution, intermediate alloy layer is special The layer formed preferably by the magnetron sputtering method using copper alloy target.The thickness of intermediate alloy layer preferably 5~500nm, more It is preferred that 10~400nm, further preferred 15~300nm, particularly preferred 20~200nm.The thickness is micro- with transmission electron Value of energy dispersion type X-ray energy spectrum analyzer (TEM-EDX) the analysis layer cross section of mirror to measure.It should be noted that can With in the inside of intermediate alloy layer, there are other sandwiched layers.The example of constituent material as sandwiched layer, can enumerate selected from by The alloy etc. of at least one kind of metal and Cu in the group of Ti, Cr, Mo, Mn, W and Ni composition.

Peeling layer 16 is the layer for the stripping that can realize carrier 12 (it is with middle layer 14).Peeling layer 16 can be organic stripping Any one of absciss layer and inorganic release layer.As the example of the organic principle used in organic peeling layer, can enumerate nitrogenous has Machine compound, organic compounds containing sulfur, carboxylic acid etc..As the example of organic compounds containing nitrogen, triazole compounds, miaow can be enumerated Azole compounds etc..On the other hand, the example as the inorganic constituents used in inorganic release layer, can enumerate Ni, Mo, Co, Cr, More than at least one of Fe, Ti, W, P, Zn metal oxide, carbon-coating etc..Wherein, from the side of release performance, film formative It sets out in face etc., it is therefore particularly preferred that peeling layer 16 is mainly more preferably mainly to be formed by carbon or hydrocarbon comprising layer made of carbon Layer, is further preferably formed by the amorphous carbon for belonging to hard carbon film.Under the above situation, peeling layer 16 (i.e. carbon-coating) passes through Concentration of carbon preferably 60 atom % or more, more preferable 70 atom % or more, further preferred 80 atom % or more, the spy of XPS measurement Not preferably 85 atom % or more.The upper limit value of concentration of carbon is not particularly limited, and can be 100 atom %, but 98 atom % or less It is real.Peeling layer 16 (especially carbon-coating) may include inevitable impurity (for example originating from ambient enviroments such as atmosphere Oxygen, carbon, hydrogen etc.).In addition, can due to anti-reflection layer 17 or the film build method of very thin layers of copper in peeling layer 16 (especially carbon-coating) Metallic atom can be mixed into.The mutual diffusivity and reactivity of carbon and carrier are small, even if the pressurization at a temperature of being subjected to more than 300 DEG C Processing etc. is also possible to prevent the formation of the metallic bond caused by the high-temperature heating between copper foil layer and joint interface, maintains to carry The stripping of body removes easy state.From inhibit excessive impurity in amorphous carbon in terms of, with aforementioned middle layer 14 at The aspect etc. of the continuous production of film is set out, and preferably the peeling layer 16 is also the layer formed by vapor phase methods such as sputterings.Peeling layer 16 thickness preferably 1~20nm, more preferable 1~10nm.The thickness is the energy dispersion type X-ray with transmission electron microscope The value that energy spectrum analysis device (TEM-EDX) analyzes layer cross section to measure.

Anti-reflection layer 17 according to expectation setting is the layer for the reflection for having the function of preventing light.Preferably, antireflection Layer 17 is made of at least one kind of metal in the group being made of Cr, W, Ta, Ti, Ni and Mo, the table of at least very thin 18 side of layers of copper Face is the aggregate of metallic particles.At this point, anti-reflection layer 17 can be the whole layer structure being made of the aggregate of metallic particles, Or the structure comprising the layer formed by the aggregate of metallic particles with the multilayer of the non-granular layer positioned at its underpart. The aggregate of the metallic particles on the surface of 18 side of very thin layers of copper of anti-reflection layer 17 is constituted due to the material of its metallic and granular Form and desired dead color is presented, which brings desired visual contrast between the wiring layer being made of copper, knot Fruit makes the identification in image inspection (such as automated graphics inspection (AOI)) improve.That is, the surface of anti-reflection layer 17 is due to gold The convex form of metal particles and the diffusing reflection that light occurs, are recognized as black.Moreover, the appropriateness of anti-reflection layer 17 and peeling layer 16 is close Conjunction property and fissility, also excellent with the adaptation of very thin layers of copper 18, to the peel resistance of developer solution when photoresist layer is formed It is excellent.From the viewpoint of above-mentioned contrast and improving identification, the gloss on the surface of 18 side of very thin layers of copper of anti-reflection layer 17 Gs (60 °) preferably 500 is spent hereinafter, more preferable 450 hereinafter, further preferred 400 hereinafter, particularly preferred 350 hereinafter, most preferably 300 or less.The lower the lower limiting value of glossiness Gs (60 °) the better, therefore is not particularly limited, but the very thin layers of copper of anti-reflection layer 17 It is 100 or more in glossiness Gs (60 °) reality on the surface of 18 sides, is more realistically 150 or more.It should be noted that coarse The mirror surface luster Gs (60 °) based on image analysis for changing particle can be according to JIS Z 8741-1997 (mirror surface lusters-survey Determine method) it is measured using commercially available Grossmeters.

More specifically, sandwiched is made of and at least very thin copper regulation metal between peeling layer 16 and very thin layers of copper 18 The surface of 18 side of layer is the anti-reflection layer 17 of the aggregate of metallic particles, so as to provide the copper with carrier of following feature Foil:1) excellent chemical-resistant resistance is presented to copper fast-etching liquid in anti-reflection layer when the wiring layer formation of centreless supporting body surface Property, and 2) image inspection after copper fast-etching when (such as automated graphics inspection (AOI)) using and anti-reflection layer contrast Bring the excellent identification of wiring layer.That is, about it is above-mentioned 1), constitute anti-reflection layer 17 be selected from Cr, W, Ta, Ti, Ni and Mo In at least one kind of metal have to the undissolved property of copper fast-etching liquid, as a result, can to copper fast-etching liquid present it is excellent Different chemical resistance.In addition, about it is above-mentioned 2), constitute anti-reflection layer 17 at least very thin 18 side of layers of copper surface metal Desired dead color is presented due to material and the granular form of the metallic in the aggregate of particle, the dead color be made of copper Desired visual contrast is brought between wiring layer, as a result, making distinguishing in image inspection (such as automated graphics inspection (AOI)) The property known improves.In addition, when the copper foil with carrier using the method manufactures the centreless supporter or printed circuit board with wiring layer, 3) when removing anti-reflection layer by fast-etching, the erosion of the wiring layer exposed under anti-reflection layer can significantly be inhibited. That is, as carrying out fast-etching at least one kind of metal in Cr, W, Ta, Ti, Ni and Mo for constituting anti-reflection layer 17 Etching solution, can use high selectivity etching solution, as a result, can inhibit or avoid the composition wiring layer caused by etching solution Copper dissolving.

In addition, from the viewpoint of improving contrast and identification and improving the uniformity of fast-etching, anti-reflection layer The surface of 17 18 side of very thin layers of copper preferably by be 10 by the determining projected area equivalent circle diameter of SEM image parsing~ The aggregate of the metallic particles of 100nm is constituted, more preferable 25~100nm, further preferred 65~95nm.Above-mentioned projected area circle The measurement of equivalent diameter can carry out as follows:It is shot with defined multiplying power (such as 50000 times) by scanning electron microscope The surface of anti-reflection layer 17 is carried out according to the image analysis of gained SEM pictures.Specifically, it is preferable that using commercially available image solution Analysis formula size distribution software and the arithmetic mean of instantaneous value for using projected area equivalent circle diameter.

Anti-reflection layer 17 is made of at least one kind of metal in Cr, W, Ta, Ti, Ni and Mo, preferably by be selected from Ta, Ti, At least one kind of metal in Ni and Mo is constituted, and is more preferably made of at least one kind of metal in Ti, Ni and Mo, most preferably by Ti It constitutes.These metals can be simple metal, or alloy.In the case of arbitrary, the substantially not oxidized (essence of these metals On be not metal oxide), will present the desired dead color of raising and the visual contrast of Cu, therefore it is preferred that, specifically, counnter attack Penetrate oxygen content preferably 0~15 atom %, more preferable 0~13 atom %, further preferred 1~10 atom % of layer 17.Arbitrary feelings Under condition, above-mentioned metal all has to the undissolved property of copper fast-etching liquid, as a result, can be presented to copper fast-etching liquid excellent Different chemical resistance.The thickness of anti-reflection layer 17 preferably 1~500nm, more preferable 10~300nm, it is further preferred 20~ 200nm, particularly preferred 30~150nm.

Very thin layers of copper 18 can be manufactured by any means, such as can be to pass through the wet types such as electroless copper method and electrocoppering The copper foil that the physical vapors such as membrane formation process, sputtering and vacuum evaporation membrane formation process, chemical gaseous phase film forming or combination thereof are formed.From It is easy from the perspective of fine-pitch of the reply based on very thinization, particularly preferred very thin layers of copper is to be steamed by sputtering method and vacuum The layers of copper that the vapor phase methods such as plating are formed, the layers of copper most preferably manufactured by sputtering method.In addition, very thin layers of copper is preferably without roughening Layers of copper when, then can also be by thick in advance as long as wiring pattern formation when will not be manufactured to printed circuit board brings obstacle Roughening, soft etching processing, cleaning treatment, redox handle and generate secondary roughening.The thickness of very thin layers of copper 18 does not have It is particularly limited to, in order to cope with above-mentioned fine-pitch, preferably 50~3000nm, more preferable 70~2500nm, further preferred 80 ~2000nm, particularly preferred 90~1500nm, particularly more preferable 120~1000nm, most preferably 150~500nm.From at film thickness The inner evenness of degree, with sheet, the productivity of web-like from the perspective of, the very thin layers of copper of the thickness in such range is preferred It is manufactured by sputtering method.

Very thin layers of copper 18 preferably has foundation with the surface (outer surface of very thin layers of copper 18) of 16 opposite side of peeling layer Arithmetic average roughness Ra, more preferable 2.0~40nm that JIS B 0601-2001 are measured, 1.0~100nm, further preferably 3.0~35nm, particularly preferred 4.0~30nm, most preferably 5.0~15nm.Such arithmetic average roughness is smaller, then is using band In the printed circuit board that the copper foil 10 of carrier manufactures, more suitably form high fineization until line/space (L/S) be 13 μm with Under/wiring pattern of the degree of 13 μm or less (such as 12 μm/12 μm~2 μm/2 μm) etc.

Very thin layers of copper 18, according to desired anti-reflection layer 17, according to (such as the closely sealed metal layer 14a of desired middle layer 14 And/or stripping auxiliary layer 14b or intermediate alloy layer) and according to desired peeling layer 16 (that is, at least very thin layers of copper 18, such as Very thin layers of copper 18 and anti-reflection layer 17) preferred development to the end face of carrier 12 and covers the end face.That is, it is preferred that not only carrier 12 Surface and end face is also at least covered by very thin layers of copper 18.Due to also covering end face, printed circuit board work can be prevented by removing It except chemical solution in sequence is to the intrusion of carrier 12, can effectively prevent when operation centreless supporter while conveying (such as roller) Side end in stripping caused by cutting, i.e. on peeling layer 16 overlay film (i.e. very thin layers of copper 18 and in the presence of Anti-reflection layer 17) notch.Film forming thickness in the carrier 12 end face of closely sealed metal layer 14a (is vertical direction relative to end face Thickness, hereinafter referred to as " end face thick ") it is preferably 2~350nm, more preferable 3~220nm, further preferred 5~150nm, especially excellent Select 6~70nm.Remove end face thickness preferably 2~350nm of auxiliary layer 14b, more preferable 3~220nm, it is further preferred 5~ 150nm, particularly preferred 6~70nm.End face thickness preferably 2~350nm of middle layer 14 as intermediate alloy layer, it is more preferable 3~ 220nm, further preferred 5~150nm, particularly preferred 6~70nm.End face thickness preferably 0~15nm of peeling layer 16, more preferable 0 ~3nm, further preferred 0~1nm, particularly preferred 0~0.5nm, most preferably 0nm.That is, most preferably not forming stripping on carrier end face Absciss layer 16.End face thickness preferably 2~350nm of anti-reflection layer 17, more preferable 3~220nm, further preferred 5~150nm, especially It is preferred that 6~70nm.End face thickness preferably 15~2800nm of very thin layers of copper 18, more preferable 20~1800nm, it is further preferred 25~ 1400nm, particularly preferred 27~1350nm, particularly more preferable 35~700nm, most preferably 45~350nm.In addition, carrier 12 It is preferably covered from the surface through-thickness (being vertical direction relative to carrier surface) of carrier 12 overlay area in end face Cover the region of 0.1mm or more, the region of more preferable 0.2mm or more, further preferred carrier 12 end face whole region.In this way, The chemical solution in the notch of the overlay film in the side end of centreless supporter, printed circuit board process can be effectively prevented to carrying The intrusion of body.

The manufacturing method of copper foil with carrier

The copper foil 10 with carrier of the present invention can manufacture as follows:Prepare above-mentioned carrier 12, on carrier 12 among formation Layer 14 (such as this 1 layer of closely sealed metal layer 14a and this 2 layers of stripping auxiliary layer 14b or intermediate alloy layers), peeling layer 16, according to the phase The anti-reflection layer 17 and very thin layers of copper 18 of prestige are to manufacture.From the viewpoint of easy fine-pitch of the reply based on very thinization, Middle layer 14, peeling layer 16, anti-reflection layer 17 (in the presence of) and the formation of each layer of very thin layers of copper 18 preferably pass through Vapor phase method carries out.As the example of vapor phase method, sputtering method, vacuum vapour deposition and ion plating method can be enumerated, from can be in 0.05nm The aspect of film thickness monitoring is carried out in the wide scope of~5000nm etc, can ensure film thickness with wide scope or even throughout entire area The aspect etc. of uniformity is set out, most preferably sputtering method.In particular, forming middle layer 14, peeling layer 16, counnter attack by sputtering method Penetrate layer 17 (in the presence of) and very thin layers of copper 18 all layers, become especially high to manufacture efficiency.Utilize vapor phase method Film forming as long as using well known gas phase film formation device according to well known condition and as long as be not particularly limited.For example, using splashing In the case of penetrating method, sputtering mode can be various sides well known to magnetron sputtering, bipolar sputtering method, opposed target as sputter method etc. Method, the aspect fast from film forming speed, productivity is high, preferably magnetron sputtering.It sputters at DC (direct current) and RF (high frequency) is any It can be carried out under power supply.In addition, though the widely known template target of target shape can also be used, but effect is used from target From the perspective of rate, it is expected that using cylindrical shape target.Hereinafter, to middle layer 14 (such as closely sealed metal layer 14a and stripping auxiliary layer This 1 layer of this 2 layers of 14b or intermediate alloy layer), peeling layer 16, anti-reflection layer 17 (in the presence of) and very thin layers of copper 18 is each The film forming using vapor phase method (preferably sputtering method) of layer illustrates.

From that can improve film thickness distribution uniformity aspect, closely sealed metal layer 14a's is excellent using the film forming of vapor phase method Choosing, using the target being made of at least one kind of metal in the group being made of Ti, Cr and Ni, in non-oxidizing atmosphere Under, it is carried out by magnetron sputtering.The purity of target preferably 99.9% or more.As the gas used in sputtering, it is preferable to use The non-active gas such as argon gas.The flow of argon gas does not limit especially as long as the suitable determination according to sputtering chamber size and membrance casting condition It is fixed.In addition, never the operating such as bad of paradoxical discharge or plasma irradiating is bad, continuously formed a film from the perspective of, Pressure when film forming is preferably carried out with the range of 0.1~20Pa.The pressure limit can be according to apparatus structure, capacity, vacuum pump Swept volume, the adjustment film forming such as the rated capacity power for the power supply that forms a film, the flow of argon gas and set.Additionally, it is contemplated that film forming Film thickness uniformity, productivity etc., sputtering power can be 0.05~10.0W/cm in the per unit area of target²In the range of fit Preferably set.

From that can improve film thickness distribution uniformity aspect, stripping auxiliary layer 14b's is excellent using the film forming of vapor phase method Choosing, is carried out under non-oxidizing atmosphere by magnetron sputtering using copper target material.The purity of copper target material preferably 99.9% More than.As the gas used in sputtering, it is preferable to use the non-active gas such as argon gas.As long as the flow of argon gas is according to sputtering chamber ruler It is very little to be just not particularly limited suitable for determination with membrance casting condition.In addition, never paradoxical discharge or plasma irradiating is bad etc. Operate it is bad, continuously formed a film from the perspective of, pressure when film forming is preferably carried out with the range of 0.1~20Pa.The pressure Power range can be according to the adjustment film forming work(such as rated capacity of apparatus structure, capacity, the swept volume of vacuum pump, the power supply that forms a film Rate, argon gas flow and set.Additionally, it is contemplated that film thickness uniformity, the productivity etc. of film forming, sputtering power can be in the every of target Unit area is 0.05~10.0W/cm²In the range of suitable for setting.

It is intermediate from film thickness distribution uniformity aspect can be improved in the case that middle layer 14 is intermediate alloy layer Layer 14 is preferably, and uses the alloys target of at least one kind of metal M and Cu in the group being made of Ti, Cr, Mo, Mn, W and Ni Material is carried out under non-oxidizing atmosphere by magnetron sputtering.The purity of copper target material preferably 99.9% or more.As in sputtering The gas used is, it is preferable to use the non-active gas such as argon gas.As long as the flow of argon gas according to sputtering chamber size and membrance casting condition and It is just not particularly limited suitable for determination.In addition, never paradoxical discharge or the plasma irradiating operating such as bad is bad, continuously From the perspective of being formed a film, pressure when film forming is preferably carried out with the range of 0.1~20Pa.The pressure limit can be according to dress Set structure, capacity, the swept volume of vacuum pump, the adjustment film forming such as the rated capacity power for the power supply that forms a film, argon gas flow and set It is fixed.Additionally, it is contemplated that film thickness uniformity, the productivity etc. of film forming, sputtering power can be 0.05 in the per unit area of target~ 10.0W/cm²In the range of suitable for setting.

It is preferable to use carbon target materials in inert atmospheres such as argons for the film forming using vapor phase method (preferably sputtering method) of peeling layer 16 Lower progress.Carbon target material is preferably made of graphite, but may be comprising inevitable impurity (for example originating from ambient enviroments such as atmosphere Oxygen, carbon).The purity of carbon target material preferably 99.99% or more, more preferable 99.999% or more.In addition, never paradoxical discharge or waiting Bad equal operating of gas ions irradiation is bad, continuously formed a film from the perspective of, pressure when film forming preferably with 0.1~ The range of 2.0Pa carries out.The pressure limit can be according to apparatus structure, the volume of capacity, the swept volume of vacuum pump, the power supply that forms a film The adjustment such as constant volume film forming power, argon gas flow and set.Additionally, it is contemplated that film thickness uniformity, the productivity etc. of film forming, sputtering Power can be 0.05~10.0W/cm in the per unit area of target²In the range of suitable for setting.

It is preferable to use by least one kind of in the group being made of Cr, W, Ta, Ti, Ni and Mo for the film forming of anti-reflection layer 17 The target that metal is constituted, is carried out by magnetron sputtering method.The purity of target preferably 99.9% or more.The utilization of anti-reflection layer 17 The film forming of magnetron sputtering method is carried out particularly preferably under the non-active gas atmospheres such as argon with 1~20Pa of pressure.Sputtering pressure is more excellent Select 2~18Pa, further preferred 3~15Pa.Such sputtering pressure is apparent high compared with the sputtering pressure of generally use, by This, surface substantially oxygen of the aggregate without making anti-reflection layer 17 of metallic particles that can be in the form of being formed uniformly and it is expected in face Change.According to above-mentioned sputtering condition, desired projected area equivalent circle diameter and desired glossiness Gs (60 °) can also be brought. In addition, also having the following advantages:Electric discharge without exception, the plasma irradiating operating such as bad are bad, can continuously form a film.It needs to illustrate , above-mentioned pressure limit control can according to apparatus structure, capacity, vacuum pump swept volume, film forming power supply it is specified Capacity etc. and adjust film forming power, the flow of argon gas carries out.As long as the flow of argon gas is according to sputtering chamber size and membrance casting condition And it is just not particularly limited suitable for determination.Additionally, it is contemplated that film thickness uniformity, the productivity etc. of film forming, sputtering power can be in target The per unit area of material is 1.0~15.0W/cm²In the range of suitable for setting.In addition, from stable membrane property (example is easy to get Such as film resistance, crystalline size) in terms of set out, preferably be film-made when bed temperature is remained centainly.Bed temperature when film forming It is preferred that adjusted in the range of 25~300 DEG C, more preferable 40~200 DEG C, it is 50~150 DEG C further preferred in the range of.

It is preferable to use copper target materials in the nonactive gas such as argon for the film forming using vapor phase method (preferably sputtering method) of very thin layers of copper 18 It is carried out under atmosphere.Copper target material is preferably made of metallic copper, can include inevitable impurity.The purity of copper target material preferably 99.9% Above, more preferable 99.99%, further preferred 99.999% or more.Temperature when forming a film in order to avoid the gas phase of very thin layers of copper 18 Degree rises, and when sputtering, the cooling body of mounting table can be arranged.In addition, never paradoxical discharge or plasma irradiating is bad Deng operate it is bad, steadily formed a film from the perspective of, pressure when film forming is preferably carried out with the range of 0.1~2.0Pa.It should Pressure limit can be according to the adjustment film forming work(such as rated capacity of apparatus structure, capacity, the swept volume of vacuum pump, the power supply that forms a film Rate, argon gas flow and set.Additionally, it is contemplated that film thickness uniformity, the productivity etc. of film forming, sputtering power can be in the every of target Unit area is 0.05~10.0W/cm²In the range of suitable for setting.

It should be noted that the middle layer 14, peeling layer 16, anti-reflection layer 17 in the end face of carrier 12 and/or very thin copper The formation of layer 18 can easily be implemented by as follows:In above-mentioned sputtering method, reveal the end face of carrier 12 in mounting table The state gone out forms a film.At this time, it is typical that in the end face of carrier 12, to form a film as the surface layer thickness of carrier 12 20%~70% thickness (end face is thick) forms a film.On the other hand, when formation peeling layer 16 etc., in end face with extremely thin thickness In the case that degree is formed a film, the side end of preferable mask carrier 12 is sputtered.As the example of the screen method, Ke Yiju Go out to utilize shielding, the shielding using masking plate of masking tape.

Centreless supporter plywood

The copper foil with carrier of the present invention can be provided in the form of centreless supporter plywood.That is, according to the present invention Preferred embodiment, provide:Has the centreless supporter plywood of the above-mentioned copper foil with carrier.It is laminated as centreless supporter The form of plate can enumerate 2 forms below.(i) the first form of centreless supporter plywood is the copper foil with carrier The form of itself.That is, being sequentially laminated with the counnter attack as needed of 14/ peeling layer 16/ of middle layer for at least single side in carrier 12 Copper foil 10 form of with carrier of 17/ very thin layers of copper 18 of layer itself is penetrated, including:It is sequentially laminated with middle layer on the two sides of carrier The form of 14/ peeling layer 16/, 17/ very thin layers of copper 18 of anti-reflection layer as needed.In the case of arbitrary, carrier 12 be glass plate, The case where metallic plate, is inferior, and in the case that carrier monomers have rigidity and can be functioned as supporter, which sets up.Example Such as, in the case of using glass as carrier 12, have:Light weight, coefficient of thermal expansion are low, upright and outspoken and surface is flat therefore can make pole The advantages that surface of thin copper layer 18 is extremely smooth.(ii) the second form of centreless supporter plywood is in carrier 12 and stripping Has the form of adhesive layer in 16 opposite side of absciss layer (i.e. the outer surface of carrier 12).Carrier 12 is by metal foil, resin film In the case of being constituted Deng the material without rigidity, the form is considered.Under the above situation, as the example of adhesive layer, it can enumerate Resin layer, (glass etc.) fibre strengthening prepreg etc..For example, it is also possible to using the counnter attack as needed of very thin layers of copper 18/ Penetrate 17/ peeling layer of layer, 16/ 14/ carrier 12 of middle layer/14/ peeling layer 16/ of adhesive layer (not illustrated)/carrier 12/middle layer The layer of 17/ very thin layers of copper 18 of anti-reflection layer as needed is constituted.It should be noted that middle layer 14 can be with from carrier 12 side There is this 2 layers of closely sealed metal layer 14a/ strippings auxiliary layer 14b successively, can be 1 layer of intermediate alloy layer, this is as aforementioned.

The manufacturing method of centreless supporter with wiring layer

The copper foil with carrier of the present invention can be used to manufacture the centreless supporter with wiring layer.Hereinafter, to band wiring layer The preferable production process of centreless supporter illustrate.The manufacturing method of the centreless supporter with wiring layer includes following work Sequence:(1) preparatory process of the copper foil with carrier;(2) formation process of photoresist layer;(3) formation process of copper electroplating layer; (4) stripping process of photoresist layer;With (5) fast-etching process.The centreless supporter with wiring layer including these processes Manufacturing method be shown schematically in Fig. 3 and 4.

(1) preparatory process of the copper foil with carrier

Prepare the copper foil 10 with carrier as supporter (with reference to (a) of Fig. 3).As above-mentioned, the copper foil 10 with carrier can be with Prepared in the form of centreless supporter plywood.That is, as above-mentioned, can be provided in the form of copper foil with carrier itself, Can by carrier 12 with have adhesive layer in 16 opposite side of peeling layer (i.e. the outer surface of carrier 12) in the form of (example Such as, 17/ peeling layer of anti-reflection layer, 16/ 14/ carrier 12 of the middle layer/adhesive layer as needed of very thin layers of copper 18/ (does not do figure Show) layer of 14/ peeling layer 16/ of/carrier 12/middle layer, 17/ very thin layers of copper 18 of anti-reflection layer as needed constitutes) prepare. It should be noted that middle layer 14 can have closely sealed metal layer 14a/ successively from carrier 12 side as shown in Figures 3 and 4 This 2 layers of auxiliary layer 14b is removed, can also be as shown in Figure 1, it is 1 layer of intermediate alloy layer, this is as aforementioned.

(2) formation process of photoresist layer

Photoresist layer 20 (with reference to (b) of Fig. 3) is formed with predetermined pattern on the surface of very thin layers of copper 18.Photoresist Preferably photosensitive film, for example, photosensitive dry film.Photoresist layer 20 can pass through cloth as defined in exposed and developed imparting Line pattern.At this point, the copper foil 10 with carrier through the invention has middle layer 14, so as to developer solution (such as carbonic acid Sodium water solution) excellent peel resistance is presented.

(3) formation process of copper electroplating layer

(the ginseng of copper electroplating layer 22 is formed in the exposing surface (part that i.e. unused photoresist layer 20 is sheltered) of very thin layers of copper 18 According to (c) of Fig. 3).Electro-coppering is not particularly limited as long as by well known method.

(4) stripping process of photoresist layer

Then, photoresist layer 20 is removed.As a result, as shown in (d) of Fig. 4, copper electroplating layer 22 is with wiring diagram Case shape remains, and the very thin layers of copper 18 for not forming the part of wiring pattern is exposed.

(5) copper fast-etching process

The unwanted part of very thin layers of copper 18 is removed by copper fast-etching, obtains the centreless for being formed with wiring layer 24 Supporter (the hereinafter referred to as centreless supporter 26 with wiring layer).At this point, the copper foil 10 with carrier has the feelings of anti-reflection layer 17 Under condition, the unwanted part of very thin layers of copper 18 is removed by copper fast-etching, so that anti-reflection layer 17 is exposed and remain (that is, Stop copper fast-etching with anti-reflection layer 17).Exposing can be etched from the over etching for avoiding copper electroplating layer 22 and certainly The aspect of very thin layers of copper 18 is set out, and preferably the fast-etching liquid uses sulfuric acid/hydrogen peroxide solution, includes sodium peroxydisulfate and mistake At least wantonly a kind of liquid in potassium sulfate.In this way, as shown in (e) of Fig. 4,22/ very thin layers of copper 18 of copper electroplating layer is to connect up Pattern-like remains, and the anti-reflection layer 17 for not forming the part of wiring pattern is not dissolved by fast-etching liquid and remained, and is become Expose on surface.At this point, constituting at least one kind of metal in Cr, W, Ta, Ti, Ni and Mo of anti-reflection layer 17 with fast to copper Therefore excellent chemical resistance can be presented to copper fast-etching liquid in the fast undissolved property of etching solution.That is, antireflection Layer 17 is not removed by copper fast-etching, and for next image inspection process and to expose state residual.

(6) image inspection etc. (arbitrary process)

After above-mentioned copper fast-etching, it is preferably carried out process:To with wiring layer centreless supporter 26 (it is specific and Speech is wiring layer 24) carry out image inspection.Image inspection typically carries out as follows:It uses optical profile type automatic shape inspection (AOI) Device irradiates defined light from light source, obtains the binary image of wiring pattern, attempt the binary image and design data figure The pattern match of picture evaluates consistency/inconsistency between the two to carry out.The image inspection preferably remains in case of presence The state that anti-reflection layer 17 exposes is set to carry out.At this point, constituting the aggregate of the metallic particles on the surface of anti-reflection layer 17 due to this Material and the granular form of metallic and desired dead color is presented, which brings the phase between the wiring layer 24 being made of copper The visual contrast of prestige, therefore the identification in image inspection (such as automated graphics inspection (AOI)) is made to improve.

After above-mentioned image inspection, as needed, it is preferably carried out process:On the centreless supporter 26 with wiring layer The electronic components 28 such as chip are carried, it is possible thereby to manufacture printed circuit board.However, it has been observed that so after forming wiring layer 24, The technique for carrying out the installation of chip is the method for referred to as RDL-First methods.It can before the installation for carrying out chip according to the technique Image inspection with each build-up wiring layer for carrying out the wiring layer of centreless supporting body surface, being laminated later, it can thus be avoided respectively The bad part of wiring layer, only in non-defective unit part chip.As a result, RDL-First methods from can be to avoid chip need not Want using for the use of set out, compared with technique i.e. Chip-First methods for stacking gradually wiring layer on the surface of chip etc., warp It is advantageous in Ji.At this point, in the case that the copper foil 10 with carrier of the present invention has anti-reflection layer 17, figure can be fully obtained As the contrast on the surface and the surface of anti-reflection layer 17 of the copper electroplating layer 22 in checking, image inspection can be carried out with high precision It looks into.For example, by optical profile type automatic shape inspection (AOI) device obtain wiring pattern binary image become it is more acurrate and It is distinct.In this way, in the manufacturing process (especially RDL-First methods) of printed circuit board, the wiring layer before being installed to chip Image inspection is carried out with high precision, thus, it is possible to improve product yield rate.In addition, about as it is contemplated by arbitrary process, The example of the electronic component 28 carried on the wiring layer of centreless supporter 26 can enumerate semiconductor element, chip capacitor, electricity Resistance body etc..As the example for the mode that electronic component carries, flip-chip mounting means, chip juncture etc. can be enumerated. Flip-chip mounting means is the installation pad for carrying out electronic component 28, the engagement with the wiring layer 24 on centreless supporter 26 Mode.Columnar electrode (pillar), solder projection etc. can be formed on the installation pad, it in a pre-installation can be in centreless supporter NCF (non-conductive film (Non-Conductive Film)) etc. of 26 24 surface adhesion of wiring layer as sealing resin film.Engagement It is carried out it is preferable to use low-melting-point metals such as solders, anisotropic conductive film etc. can also be used.Chip engages bonding side Formula is that the mode with the face of installation pad face opposite side of electronic component 28 is bonded to the wiring layer 24 on 26 surface of centreless supporter. It is preferable to use paste, the films of the resin combination for belonging to the inorganic filler comprising heat reactive resin and thermal conductivity in the bonding.

The manufacturing method of printed circuit board

The centreless supporter with wiring layer of the present invention can be used to manufacture printed circuit board.Hereinafter, to printed circuit board Preferable production process illustrate.The manufacturing method of the printed circuit board includes following process:(1) the centreless branch with wiring layer The manufacturing process of support body;(2) production process of the laminated body with lamination layer;(3) separation process of the laminated body with lamination layer; With the manufacturing procedure of (4) multilayer circuit board.The manufacturing method of printed circuit board including these processes is shown schematically in Fig. 3~5 (especially Fig. 5).

(1) manufacturing process of the centreless supporter with wiring layer

The centreless supporter 26 with wiring layer is manufactured by the method for aforementioned present invention.That is, the printed circuit board of the present invention Manufacturing method include the above-mentioned centreless supporter with wiring layer manufacturing method a series of process, herein omit repeat Explanation.

(2) production process of the laminated body with lamination layer

Have in the formation of the centreless supporter 26 with wiring layer and form lamination layer 30 on the face of wiring layer 24, makes band lamination The laminated body 32 of layer (with reference to (g) of Fig. 5).It should be noted that in Fig. 5, the details of lamination layer 30 is shown, but as long as adopting It is just not particularly limited with the composition of the well known build-up wiring layer used in general printed circuit board.

(3) separation process of the laminated body with lamination layer

The peeling layer 16 of laminated body 32 with lamination layer is detached, the multilayer circuit board 34 for including lamination layer 30 is obtained.That is, Carrier 12, middle layer 14 and peeling layer 16 are removed and removed.In the separation process, physical separation, Chemical Decomposition may be used Deng preferably physics stripping.Physical partition method be with hand, fixture tool, machinery etc. by carrier 12 etc. from the stripping of lamination layer 30 to Carry out the method for isolated multilayer circuit board 34 (with reference to (h) of Fig. 5).At this point, the copper foil 10 with carrier through the invention With middle layer 14, excellent stability can be carried out for the mechanical stripping intensity band of carrier 12.As a result, can by carrier 12 with Middle layer 14 and peeling layer 16 are easily peeled off together.

(4) manufacturing procedure of multilayer circuit board

Multilayer circuit board 34 is processed to obtain printed circuit board 36 ((i) of Fig. 5).At this point, in multilayer circuit board 34 On there are anti-reflection layer 17 in the case of, preferably anti-reflection layer 17 is removed by fast-etching.The fast-etching for example such as with Under table 1 exemplified by like that, etching solution appropriate is preferably selected according to the metal for constituting anti-reflection layer 17 and is carried out.In table 1 Representative etching solution is shown, but is not limited to these, acid, the type of ammonium salt, concentration, temperature etc. can be by recorded in table 1 Condition is suitable for change.

[Table 1]

Table 1

It therefore can so as to selectively carry out fast-etching to anti-reflection layer 17 by using such etching solution Significantly to inhibit the erosion in the wiring layer 24 (it is made of copper) of 17 times exposings of anti-reflection layer.That is, as to constituting At least one kind of metal in Cr, W, Ta, Ti, Ni and Mo of anti-reflection layer 17 carries out the etching solution of fast-etching, can use The etching solution of high selectivity, as a result, can inhibit or avoid constituting the dissolving caused by the etching solution of the copper of wiring layer 24.

Printed circuit board 36 shown in fig. 5 can be processed outer layer by various techniques.For example, can be in printing electricity As the insulating layer and wiring layer of build-up wiring floor on the wiring layer 24 of road plate 36 and then using the stacking of the arbitrary number of plies, or connecting up The surface of layer 24 forms solder mask, can also implement to plate Ni-Au, OSP processing (water-soluble pre- scaling powder processing, Organic Solderability Preservative) etc. surface treatment as outer layer pad.In turn, can be arranged in outer layer pad Columnar pillar etc..Can not have suitable for the well known technique used in additional general printed circuit board in the case of arbitrary It is particularly limited to.

Embodiment

The present invention is further specifically described according to example below.

Example 1

(1) making of the copper foil with carrier

As shown in Figure 1, form a film closely sealed metal layer 14a, stripping auxiliary layer successively on the sheet glass as carrier 12 14b, peeling layer 16 and very thin layers of copper 18 and make the copper foil 10 with carrier.Specific step is as described below.It needs to illustrate Be the arithmetic average roughness Ra referred in example below be according to JIS B 0601-2001 with non-planar contact surfaces shape survey Determine the value of machine (Zygo Co. Ltd. system NewView5032) measurement.

The preparation of (1a) carrier

Prepare the sheet glass (material of 700 μm of the thickness on the surface with arithmetic average roughness Ra 0.5nm:Alkali-free glass Glass, product name:OA10, Nippon Electric Glass Co., Ltd's system).

The state for sheltering the end face of carrier 12 with stainless steel plate is formed, it is such as following, carry out various layers by sputtering It is formed.

The formation of (1b) closely sealed metal layer

Device below and under the conditions of, formed on the surface by sputtering at carrier 12 and be used as closely sealed metal layer 14a's The titanium layer of thickness 100nm.

Device:One chip magnetic control sputtering device (Tokki Corporation systems)

Target:The Ti targets (purity 99.999%) of 8 inches of diameter (203.2mm)

Final vacuum Pu:Less than 1 × 10^-4Pa

Carrier gas:Ar (flows:100sccm)

Sputtering pressure:0.35Pa

Sputtering power:2000W(6.2W/cm²)

Temperature when film forming:40℃

(1c) removes the formation of auxiliary layer

Device below and under the conditions of, remove auxiliary layer 14b's by sputtering on closely sealed metal layer 14a to be formed be used as The layers of copper of thickness 100nm.

Device:One chip DC sputter equipments (Canon Tokki Corporation systems, MLS464)

Target:The copper target material (purity 99.98%) of 8 inches of diameter (203.2mm)

Final vacuum Pu:Less than 1 × 10^-4Pa

Gas:Argon gas (flow:100sccm)

Sputtering pressure:0.35Pa

Sputtering power:2000W(6.2W/cm²)

Temperature when film forming:40℃

The formation of (1d) peeling layer

Device below and under the conditions of, the thickness for being used as peeling layer 16 is formed on stripping auxiliary layer 14b by sputtering at The amorphous carbon layer of 3nm.

Device:One chip DC sputter equipments (Canon Tokki Corporation systems, MLS464)

Target:The carbon target material (purity 99.999%) of 8 inches of diameter (203.2mm)

Final vacuum Pu:Less than 1 × 10^-4Pa

Carrier gas:Ar (flows:100sccm)

Sputtering pressure:0.35Pa

Sputtering power:100W(0.3W/cm²)

Temperature when film forming:40℃

The formation of (1e) anti-reflection layer

Device below and under the conditions of, the thickness for being used as anti-reflection layer 17 is formed on the surface by sputtering at peeling layer 16 Spend the titanium layer of 100nm.

Device:One chip DC sputter equipments (Canon Tokki Corporation systems, MLS464)

Target:The titanium target material (purity 99.999%) of 8 inches of diameter (203.2mm)

Carrier gas:Ar (flows:100sccm)

Final vacuum Pu:Less than 1 × 10^-4Pa

Sputtering pressure:12Pa

Sputtering power:2000W(6.2W/cm²)

The formation of (1f) very thin layers of copper

Device below and under the conditions of, the very thin layers of copper 18 of film thickness 300nm is formed by sputtering on anti-reflection layer 17. The very thin layers of copper of gained 18 is 3nm with the arithmetic average roughness (Ra) on the surface (i.e. outer surface) of 16 opposite side of peeling layer.

Device:One chip DC sputter equipments (Canon Tokki Corporation systems, MLS464)

Final vacuum Pu:Less than 1 × 10^-4Pa

Carrier gas:Ar (flows:100sccm)

Sputtering pressure:0.35Pa

Sputtering power:2000W(6.2W/cm²)

Temperature when film forming:40℃

The measurement of (1g) composition analysis

As the sample for composition analysis etc., pass through the closely sealed metal layer with the copper foil with carrier obtained among the above 14a, stripping auxiliary layer 14b, the manufacturing condition same with the manufacturing condition of anti-reflection layer 17 of peeling layer 16, are produced as follows sample respectively Product:It is simply formed with the sample of closely sealed metal layer 14a on the glass sheet, is simply formed with the sample of stripping auxiliary layer 14b on the glass sheet Product, the sample for being simply formed with peeling layer 16 on the glass sheet and the sample for being simply formed with anti-reflection layer 17 on the glass sheet.To each Sample, such as following carry out composition analysis, to hold the composition of each layer.

The closely sealed metal layers of <, the composition analysis > for removing auxiliary layer and anti-reflection layer

For closely sealed metal layer 14a, stripping auxiliary layer 14b and anti-reflection layer 17, the monitoring sample of surface analysis is made, Elemental analysis is carried out by TOF-SIMS (time of flight secondary ion massspectrometry analysis).The measurement is existed by constant-current mode It is carried out under conditions of 800V-3mA.As a result, the composition difference of closely sealed metal layer 14a, stripping auxiliary layer 14b and anti-reflection layer 17 As shown below.Closely sealed metal layer 14a:Ti:92.5 atom %, O:7.5 atom %

Remove auxiliary layer 14b:Cu:99 atom %, O:1 atom %

Anti-reflection layer 17:Ti:99.6 atom %, O:0.4 atom %

The composition analysis > of < peeling layers

For peeling layer 16 (i.e. carbon-coating), elemental analysis is carried out by XPS, measures concentration of carbon.As a result, peeling layer 16 Concentration of carbon is 93 atom % (C+O=100%).

The measurement > of the projected area equivalent circle diameter on < anti-reflection layers surface

Sampling has just formed the sample after anti-reflection layer 17, by scanning electron microscope with 50000 times of shooting counnter attacks The surface for penetrating layer 17 obtains SEM image.The image analysis of binary image is carried out as the SEM pictures by obtained by measure.The image Image analysis formula size distribution software (MountechCo., Ltd. system, Mac-VIEW) is used in parsing.It measures with arbitrary 50 A above particle is object, measures projected area equivalent circle diameter for each particle, calculates its arithmetic mean of instantaneous value.As a result, The projected area equivalent circle diameter on the surface of anti-reflection layer 17 is 60nm.

Example 2

In order to form nickel layer instead of titanium layer as closely sealed metal layer 14a, it is nickel target (purity to make sputtering target material 99.999%) making and evaluation of the copper foil with carrier, in addition to this, are carried out similarly with example 1.The results are shown in Table 2.It needs Illustrate, very thin layers of copper 18 is 3.7nm with the arithmetic average roughness Ra on the surface of 16 opposite side of peeling layer.Except closely sealed gold The composition for belonging to each layer other than layer 14a is substantially same with example 1.The group of closely sealed metal layer 14a becomes Ni:99.5 atom %, O:0.5 Atom %.

Example 3

In order to form layers of chrome instead of titanium layer as closely sealed metal layer 14a, it is chromium target (purity to make sputtering target material 99.999%) making and evaluation of the copper foil with carrier, in addition to this, are carried out similarly with example 1.The results are shown in Table 2.It needs Illustrate, very thin layers of copper 18 is 3.5nm with the arithmetic average roughness Ra on the surface of 16 opposite side of peeling layer.Except closely sealed gold The composition for belonging to each layer other than layer 14a is substantially same with example 1.The group of closely sealed metal layer 14a becomes Cr:98.0 atom %, O:2.0 Atom %.

Example 4

As carrier 12, prepare that there is arithmetic average roughness Ra:The alumina plate of 1000 μm of the thickness on 0.2 μm of surface (product name:A-476, Kyocera Corporation systems), its surface is handled by CMP (chemically mechanical polishing) method, To make the roughness on surface be in addition to this Ra1.0nm is carried out similarly the making and evaluation of the copper foil with carrier with example 1. The results are shown in Table 2.It should be noted that the arithmetic average roughness with the surface of 16 opposite side of peeling layer of very thin layers of copper 18 Ra is 2.1nm.The composition of each layer is substantially same with example 1.

Example 5

As carrier 12, it is ready to pass through surface grinding processing and there is arithmetic average roughness Ra:The thickness on the surface of 1.0nm The yttria stabilized zirconia plate (10 weight % of yttrium oxide) (Xin Guang societies of Co., Ltd. system) of 500 μm of degree, in addition to this, with example 1 is carried out similarly the making and evaluation of the copper foil with carrier.The results are shown in Table 2.It should be noted that very thin layers of copper 18 with The arithmetic average roughness Ra on the surface of 16 opposite side of peeling layer is 2.2nm.The composition of each layer is substantially same with example 1.

Example 6(comparison)

Closely sealed metal layer 14a is not formed and in addition to this stripping auxiliary layer 14b is carried out similarly the copper with carrier with example 1 The making and evaluation of foil.The results are shown in Table 2.It should be noted that the surface with 16 opposite side of peeling layer of very thin layers of copper 18 Arithmetic average roughness Ra be 1.0nm.The composition of each layer is substantially same with example 1.

Example 7(comparison)

In order to form aluminium layer instead of the titanium layer as closely sealed metal layer 14a, it is aluminium target (purity to make sputtering target material 99.999%) making and evaluation of the copper foil with carrier, in addition to this, are carried out similarly with example 1.The results are shown in Table 2.It needs Illustrate, very thin layers of copper 18 is 4.0nm with the arithmetic average roughness Ra on the surface of 16 opposite side of peeling layer.Except closely sealed gold The composition for belonging to each layer other than layer 14a is substantially same with example 1.The group of closely sealed metal layer 14a becomes Al:98 atom %, O:2 is former Sub- %.

Example 8(comparison)

It does not form stripping auxiliary layer 14b and is in addition to this carried out similarly the making and evaluation of the copper foil with carrier with example 1. The results are shown in Table 2.It should be noted that the arithmetic average roughness with the surface of 16 opposite side of peeling layer of very thin layers of copper 18 Ra is 2.2nm.The composition of each layer is substantially same with example 1.

Example 9(comparison)

Closely sealed metal layer 14a is not formed, in addition to this, the making and evaluation of the copper foil with carrier is carried out similarly with example 1. The results are shown in Table 2.It should be noted that the arithmetic average roughness with the surface of 16 opposite side of peeling layer of very thin layers of copper 18 Ra is 3.1nm.The composition of each layer is substantially same with example 1.

Example 10(comparison)

It is replaced as the layers of copper for removing auxiliary layer 14b to form nickel layer, it is nickel target (purity to make sputtering target material 99.999%) making and evaluation of the copper foil with carrier, in addition to this, are carried out similarly with example 1.The results are shown in Table 2.It needs Illustrate, very thin layers of copper 18 is 2.5nm with the arithmetic average roughness Ra on the surface of 16 opposite side of peeling layer.It is auxiliary except removing Help the composition of each layer other than layer 14b substantially same with example 1.Removing the group of auxiliary layer 14b becomes Ni:99.0 atom %, O:1.0 Atom %.

Example 11~13

Molybdenum layer (example 11), tungsten layer (example 12) or manganese layer (example 13) replacement are formed as the titanium of closely sealed metal layer 14a using sputtering Layer, in addition to this, the making and evaluation of the copper foil with carrier is carried out similarly with example 1.The results are shown in Table 2.

Example 14~24(only example 18 and 19 is comparative example)

In example 1, forms the intermediate alloy layer formed shown in the table 3 as the middle layer 14 of single layer and replace closely sealed metal layer 14a and this 2 layers of stripping auxiliary layer 14b, in addition to this, the making and evaluation of the copper foil with carrier is carried out similarly with example 1.As a result As shown in table 3.

Example 25~29

I) do not implement masking in the end face of carrier 12 and carry out closely sealed metal layer 14a, stripping auxiliary layer 14b, anti-reflection layer 17 and very thin layers of copper 18 formation;With ii) implement to carry out the formation of peeling layer 16 using the masking of stainless steel plate, make end Thickness (end face is thick) variation of peeling layer 16 in face, in addition to this, the making of the copper foil with carrier is carried out similarly with example 1. As a result, the thickness (end face is thick) of each layer in the end face of carrier 12 is such as following.

Closely sealed metal layer 14a:(end face is thick for titanium layer:35nm)

Remove auxiliary layer 14b:(end face is thick for layers of copper:35nm)

Peeling layer 16:Carbon-coating (various end faces shown in table 4 are thick)

Anti-reflection layer 17:(end face is thick for titanium layer:38nm)

Very thin layers of copper 18:(end face is thick for layers of copper:100nm)

Example 30

I) do not implement masking in the end face of carrier 12 and carry out the middle layer 14 as intermediate alloy layer, 17 and of anti-reflection layer The formation of very thin layers of copper 18;With ii) implement to carry out the formation of peeling layer 16 using the masking of stainless steel plate, make in end face Peeling layer 16 thickness (end face thick) as follows, in addition to this, the making of the copper foil with carrier is carried out similarly with example 1

Middle layer 13 (intermediate alloy layer):Cu-Mn alloy-layers (element ratio Cu:Mn=95:5, end face is thick:35nm)

Peeling layer 16:(end face is thick for carbon-coating:0nm)

Anti-reflection layer 17:(end face is thick for titanium layer:38nm)

Very thin layers of copper 18:(end face is thick for layers of copper:100nm)

Various evaluations

For the copper foil with carrier of example 1~30, as shown below, various evaluations are carried out.Evaluation result such as 2~4 institute of table Show.

< evaluations 1:Peel resistance > of the very thin layers of copper to developer solution

The surface of the very thin layers of copper of each copper foil with carrier is handled with the dilute sulfuric acid of 0.05mol/L, carries out surface The removal of oxidation film washed and dried later.Later, in the surface adhesion photosensitive dry film of very thin layers of copper, to assign The mode of the pattern of line/space (L/S)=5 μm/5 μm is exposed and develops.Development is following to be carried out:Use 1.0 weight % carbon Acid sodium aqueous solution is carried out 2 minutes as developer solution at 25 DEG C in the way of spray.To after development, developer solution to very thin copper Very thin layers of copper caused by the immersion of interface layer (especially between peeling layer and closely sealed metal layer) between layer and carrier The presence or absence of stripping or degree are evaluated.Gained evaluation result is graded with benchmark below.

Evaluate AA:The stripping of very thin layers of copper is not observed.

Evaluate A:Very thin layers of copper is removed with 3 μm of sizes below of diameter.

Evaluate B:Very thin layers of copper is removed with 50 μm of sizes below of diameter.

Evaluate C:Very thin layers of copper is removed with size of 50 μm more than diameter.

< evaluations 2:The fissility > of the very thin layers of copper of carrier-

In the following manner, after the Reflow Soldering to the progress of the copper foil with carrier as thermal history and Vacuum Heat pressurize Peel strength is measured.After the plate electrolytic copper plating for implementing 18 μm of thickness to 18 side of very thin layers of copper of the copper foil 10 with carrier, make For thermal history 1, the heat treatment for assuming the Reflow Soldering (being kept for 2 minutes at 260 DEG C or more) of electronic unit installation, natural cooling are carried out To room temperature.Later, as thermal history 2, at 220 DEG C, with 30kgf/cm²Pressure pressurize 90 minutes.For gained copper clad layers Lamination measures peel strength when removing the copper electroplating layer being integrally formed with very thin layers of copper 18 according to JIS C 6481-1996 (gf/cm).At this point, measuring, width is set as 50mm, measured length is set as 20mm.With benchmark below to the obtained peel strength (average value) grades.

Evaluate A:Peel strength is 2~10gf/cm

Evaluate B:Peel strength is 1~30gf/cm (wherein, not including 2~10gf/cm)

Evaluate C:Peel strength is less than 1gf/cm or more than 30gf/cm

< evaluations 3:The evaluation > of overlay film notch in centreless supporter end

After implementing electro-coppering for the centreless supporter used in evaluation 1, carried out with Sulfuric-acid-hydrogen-peroxide aqueous solution very thin The fast-etching of layers of copper, to form the centreless supporter with wiring pattern.For centreless supporter of the gained with wiring pattern, Measure the maximum width of the notch of the overlay film (that is, very thin layers of copper and anti-reflection layer) on the peeling layer in centreless supporter end (mm), it is graded with following benchmark.As a result as shown in table 2~4.

Evaluate AA:Less than 0.1mm (best)

Evaluate A:0.1mm is less than 1mm (good)

Evaluate B:1mm (can allow) less than 2mm

Evaluate C:2mm or more (can not)

< evaluations 4:The evaluation > of the fine pattern formative of buried wiring layer

For the centreless supporter with wiring pattern obtained in evaluation 3, stacks gradually prepreg and copper foil and cure, from And form the laminated body with lamination layer.Later, the laminated body with lamination layer is mechanically detached by peeling layer, is obtained Include the multilayer circuit board of lamination layer.Later, it is based on condition shown in aforementioned table 1 and fast-etching, observation is carried out to anti-reflection layer It is embedded to the character of the wiring layer of lamination layer, is graded according to benchmark below.As a result as shown in tables 2 and 3.Buried wiring is not Good counting is as follows:It is limited to 8mm × 8mm square by 1, is counted bad when the observation the piece number in each example being made to be 336 Rate.It should be noted that as the carrier side of generation when bad mode is the stripping of very thin layers of copper, removes centreless supporter Short circuit etc. caused by the stripping of the closely sealed metal layer, stripping auxiliary layer of metal.

Evaluate AA:Fraction defective is less than 5 number % (best)

Evaluate A:Fraction defective is 5 number % less than 10 number % (good)

Evaluate B:Fraction defective is that 10 number % (can) less than 20 number %

Evaluate C:Fraction defective be 20 number % less than 50 number % (can not)

< evaluations 5:Chemical solution invades the evaluation > of width

For the centreless supporter with wiring pattern obtained in evaluation 3, by the prepreg of size 100mm × 100mm (200 μm of Panasonic Corporation FR-4, thickness) stacking makes prepreg cure, and makes printed circuit board.For institute Printed circuit board is obtained, handled using the desmearing of sodium permanganate solution, measures medicament intrusion width (mm) as expressionization Learn the index of solution intrusion volume.

Desmearing processing using Rohm and Haas Electronics Materials Co., Ltd treatment fluid as shown below, successively Managed everywhere in following to implement.

[Rong Zhangchuli ]

Treatment fluid:Circuposit MLB CONDITIONER 211-120mL/L and

Circuposit Z-100mL/L

Treatment conditions:It is impregnated 5 minutes with 75 DEG C

[Permanganic acid handles ]

Treatment fluid:Circuposit MLB Promoter 213A-110mL/L and

Circuposit MLB Promoter 213B-150mL/L

Treatment conditions:It is impregnated 5 minutes with 80 DEG C

[Zhong Hechuli ]

Treatment fluid:Circuposit MLB Neutralizer 216-2-200mL/L

Treatment conditions:It is impregnated 5 minutes with 45 DEG C

It grades to the chemical solution intrusion width (mm) of measurement according to benchmark below.As a result as shown in table 2~4.

Evaluate AA:Less than 0.1mm (best)

Evaluate A:0.1mm is less than 0.5mm (good)

Evaluate B:0.5mm (can allow) less than 2mm

Evaluate C:2mm or more (can not)

[Table 2]

[Table 3]

[Table 4]

Table 4

Claims

1. a kind of copper foil with carrier, has:

Carrier;

Middle layer is set on the carrier, wherein the surface of the carrier side contain 1.0at% or more selected from by Ti, At least one kind of metal in the group of Cr, Mo, Mn, W and Ni composition, and contain 30at% or more with the surface of the carrier opposite side Cu;

Peeling layer is set in the middle layer;With,

Very thin layers of copper is set on the peeling layer.

2. the copper foil according to claim 1 with carrier, wherein the middle layer has the thickness of 5~1000nm.

3. the copper foil according to claim 1 or 2 with carrier, wherein the middle layer includes:

Closely sealed metal layer is set on the carrier, by least 1 in the group being made of Ti, Cr, Mo, Mn, W and Ni Kind metal is constituted;With,

Auxiliary layer is removed, is set on the closely sealed metal layer, is made of copper.

4. the copper foil according to claim 3 with carrier, wherein the closely sealed metal layer has the thickness of 5~500nm.

5. the copper foil according to claim 3 or 4 with carrier, wherein the stripping auxiliary layer has the thickness of 5~500nm Degree.

6. the copper foil according to claim 1 or 2 with carrier, wherein the middle layer is intermediate alloy layer, the centre Alloy-layer by least one kind of metal in the group being made of Ti, Cr, Mo, Mn, W and Ni content be 1.0at% or more and The copper alloy that Cu contents are 30at% or more is constituted.

7. the copper foil according to claim 6 with carrier, wherein the intermediate alloy layer has the thickness of 5~500nm.

8. the copper foil according to any one of claims 1 to 7 with carrier, wherein the peeling layer is mainly comprising carbon.

9. according to the copper foil according to any one of claims 1 to 8 with carrier, wherein the peeling layer has 1~20nm's Thickness.

10. according to the copper foil according to any one of claims 1 to 9 with carrier, wherein the very thin layers of copper with the stripping The surface of absciss layer opposite side has arithmetic average roughness Ra measured according to JIS B 0601-2001,1.0~100nm.

11. according to the copper foil according to any one of claims 1 to 10 with carrier, wherein the middle layer of the carrier The surface of side has arithmetic average roughness Ra measured according to JIS B 0601-2001,0.1~70nm.

12. the copper foil with carrier according to any one of claim 1~11, wherein the carrier is by glass or ceramics It constitutes.

13. the copper foil with carrier according to any one of claim 1~12, wherein the carrier is made of glass.

14. the copper foil with carrier according to any one of claim 1~13, wherein at least described very thin layers of copper extends Go out the end face of the carrier and covers the end face.

15. a kind of manufacturing method of the centreless supporter with wiring layer comprising following process:

Prepare process of the copper foil with carrier described in any one of claim 1~14 as supporter;

In the process that the surface of the very thin layers of copper forms photoresist layer with defined pattern;

In the process that the exposing surface of the very thin layers of copper forms copper electroplating layer;

The process that the photoresist layer is removed;With,

The unwanted part of the very thin layers of copper is removed by copper fast-etching, obtains the centreless support for being formed with wiring layer The process of body.

16. a kind of manufacturing method of printed circuit board comprising following process:

The process for manufacturing the centreless supporter with wiring layer by method of claim 15;

Have in the formation of the centreless supporter with wiring layer and form lamination layer on the face of the wiring layer, to make band product The process of laminated body layer by layer;

By the laminated body with the lamination layer stripping layer separation, the work of the multilayer circuit board comprising the lamination layer is obtained Sequence;With,

The multilayer circuit board is processed to obtain the process of printed circuit board.